EP0058335B1 - Diamines, process for their preparation, and their use as chain extenders in the production of polyurethane plastics - Google Patents
Diamines, process for their preparation, and their use as chain extenders in the production of polyurethane plastics Download PDFInfo
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- EP0058335B1 EP0058335B1 EP82100699A EP82100699A EP0058335B1 EP 0058335 B1 EP0058335 B1 EP 0058335B1 EP 82100699 A EP82100699 A EP 82100699A EP 82100699 A EP82100699 A EP 82100699A EP 0058335 B1 EP0058335 B1 EP 0058335B1
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- mixture
- diamines
- isomers
- present
- homologues
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- 150000004985 diamines Chemical class 0.000 title claims description 21
- 238000000034 method Methods 0.000 title claims description 20
- 229920002635 polyurethane Polymers 0.000 title claims description 14
- 239000004814 polyurethane Substances 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 229920003023 plastic Polymers 0.000 title claims description 7
- 239000004033 plastic Substances 0.000 title claims description 7
- 238000002360 preparation method Methods 0.000 title claims description 5
- 239000004970 Chain extender Substances 0.000 title description 6
- 239000000203 mixture Substances 0.000 claims description 38
- 238000006396 nitration reaction Methods 0.000 claims description 11
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical group CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 13
- 150000004996 alkyl benzenes Chemical class 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229920002396 Polyurea Polymers 0.000 description 3
- -1 aromatic nitro compounds Chemical class 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 230000000802 nitrating effect Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YSXYETTXHFLEGZ-UHFFFAOYSA-N 12,12-dinitrododecylbenzene Chemical compound [O-][N+](=O)C([N+]([O-])=O)CCCCCCCCCCCC1=CC=CC=C1 YSXYETTXHFLEGZ-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 150000005182 dinitrobenzenes Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 150000004998 toluenediamines Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3237—Polyamines aromatic
- C08G18/324—Polyamines aromatic containing only one aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/06—Compounds containing nitro groups bound to a carbon skeleton having nitro groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
Definitions
- the present invention relates to new alkyl-substituted phenylenediamines which are present as a homolog and isomer mixture, a process for their preparation and their use as chain extenders in the production of polyurethane plastics.
- Aromatic diamines represent a known class of compounds.
- the isomeric phenylene and toluenediamines have the disadvantage that they are substances which are crystalline at room temperature, and which have therefore found little use in practice as reactants for organic polyisocyanates, for example as chain extenders in the production of polyurethane plastics.
- US Pat. No. 2,934,571 describes the production of long-chain dinitro-alkyl-benzenes which can be processed further to give the corresponding diamines in accordance with US Pat. No. 2,986,576.
- the alkylbenzenes used as starting material according to US Pat. No. 2,934,571 are largely defined compounds which in particular have a branched oligopropylene side chain.
- a special nitration process is proposed in the prior publication, since conventional nitration processes obviously fail when nitrating the hydrocarbons to be used according to the prior publication to the corresponding dinitro-alkyl-benzenes.
- the invention relates to diamines of the formula present as a mixture of homologs and isomers in which
- R represents a saturated, straight-chain, aliphatic hydrocarbon radical with 8-15 carbon atoms, and which by dinitration and subsequent hydrogenation of the nitro groups of hydrocarbons of the formula present as a mixture of homologs and isomers have been obtained which, at 1,013 mbar, have a boiling range in accordance with ASTM D 86 of 10-50 ° C. within the temperature range of 270 ° C.-330 ° C.
- the invention also relates to a process for the preparation of these new diamines, which is characterized in that hydrocarbons of the last-mentioned type present as a homolog and isomer mixture in a manner known per se by nitration in dinitro compounds of the formula transferred and then hydrogenated in a manner known per se to the corresponding diamines.
- the present invention also relates to the use of the new diamines as chain extenders in the production of polyurethane plastics by the isocyanate polyaddition process.
- alkylbenzene mixtures are prepared in a manner known per se by alkylating benzene with the corresponding technical, linear olefin mixtures, such as, for example, the corresponding technical oligoethylene mixtures or other linear oligo-olefins, or with the corresponding technical linear alkyl chloride mixtures, as for example in Kirk-Othmer, Encyclopedia of Chemical Technology, third edition, Vol. 2, (1978) on pages 50 to 61.
- the alkylbenzenes are converted into the corresponding dinitro compounds by a nitration reaction known per se, for example in the temperature range from 10 to 30 ° C. using, for example, 2-3 moles of concentrated nitric acid per mole of alkylbenzene, the nitric acid in the form of a mixture with concentrated sulfuric acid ( Nitrating acid) is used.
- a nitration reaction known per se, for example in the temperature range from 10 to 30 ° C.
- the nitric acid in the form of a mixture with concentrated sulfuric acid ( Nitrating acid) is used.
- the alkyl-substituted dinitrobenzenes obtained in this way, according to nuclear magnetic resonance measurements, over 95% of all nitro groups are arranged in a meta position to one another.
- 1-alkyl-2,4-dinitrobenzene in 2,6-free form could also be used for the next stage of the process according to the invention, as is the case, for example, by two-stage nitration of alkylbenzene via the intermediate stage of the initially isolated 1-alkyl-4 -nitrobenzene is available.
- the dinitroalkylbenzene mixtures are obtained without disruptive mononitro fractions, as evidenced by the content of nitro groups determined in each case, and by thin-layer chromatographic studies of the nitration products.
- the dintroalkylbenzene mixtures thus obtained are therefore excellently suitable for direct further processing to give the diamines according to the invention, without the need for complex purification operations which, in particular in the case of removal of the mononitro compounds by distillation under technical conditions, involve incalculable dangers because of the easy decomposability of aromatic nitro compounds under thermal stress would bring themselves.
- the next stage of the process according to the invention consists in the known hydrogenation of the nitro groups to the corresponding primary amino groups, for example using Raney nickel as a hydrogenation catalyst at, for example, 20-60 ° C. and a hydrogen pressure of, for example, 20 to 40 bar.
- the diamines of the above formula according to the invention obtained in this hydrogenation naturally correspond with regard to the position of the amino groups to the statements made with regard to the position of the nitro groups and with regard to the nature of the radical R to the descriptions in the description of the Atkytbe to be used for their preparation . nzoten made statements.
- the diamines according to the invention are substances which are liquid at room temperature and which show no tendency to crystallize and which contain no disruptive proportions of monofunctional amines. For this reason, the compounds according to the invention are valuable chain extenders in the production of polyurethane plastics by the isocyanate polyaddition process.
- the new diamines are used according to the invention, they are generally mixed with NCO prepolymers while maintaining an NCO / NH 2 equivalent ratio of 0.7: to 1.3: 1, preferably 0.9 1 to 1.1: 1 reacted in a known manner.
- the NCO prepolymers to be used here are reaction products known per se of the diisocyanates known per se in polyurethane chemistry with deficient amounts of polyhydroxyl compounds, in particular polyhydroxy polyesters or polyhydroxy polyethers having a molecular weight between 300 and 10,000, preferably 1,000 and 4,000 and a (in the case of using mixtures of polyhydroxyl compounds medium) hydroxyl functionality of 2 to 8, preferably 2 to 3.
- the new diamines according to the invention can also advantageously be used a one-step process in the production of polyurethanes can be used by admixing them with a polyhydroxyl compound or a mixture of polyhydroxyl compounds of the type mentioned by way of example, whereupon this mixture with the known polyisocyanates of polyurethane chemistry while maintaining an equivalent ratio between isocyanate groups and groups reactive to isocyanate groups of approx 0.8: 1 to 1.2: 1, in particular 1: 1, is converted to the high molecular weight polyurethane.
- a homologue mixture of linear alkyl benzenes is used, the alkyl chains of which have a length of 10 to 13 C atoms and an average chain length of about 12 C atoms.
- the homolog mixture boils according to ASTM D 86 at 1,013 mbar between approx. 283 and 313 ° C, with approx. 50 volume percent passing to 296 ° C. It is a reaction product of benzene with a mixture of linear C 10 -C 13 olefins.
- a mixture of 1,136 ml of 98% nitric acid and 1,584 ml of 96% sulfuric acid is added dropwise to 1.97 kg of alkylbenzene mixture with cooling so that the internal temperature is 10 to 15 ° C. After the dropping has ended, the mixture is stirred at 25 to 30 ° C. for 3 hours. The organic phase is subsequently poured onto 10 kg of ice, washed neutral with sodium bicarbonate solution and washed again with water. The organic phase is separated off and any remaining water is largely removed by centrifugation. The liquid dinitroalkylbenzene mixture thus obtained was fed to the next reaction stage without further purification.
- Dinitrododecylbenzene was prepared in accordance with Example V of US Pat. No. 2,934,571.
- the crude product had an N0 2 content of only 18.6 percent by weight.
- the preliminary ver A product with an NO 2 content of 20.0 percent by weight was available to the public.
- Thin-layer chromatographic studies show significant proportions of mononitro compounds, the presence of which can be derived from the low NO 2 content mentioned.
- 500 g of this NCO prepolymer are briefly degassed at about 55 ° C. and mixed with 53 g of the diamine mixture according to the invention from Example 1 within 30 seconds. After a casting time of 4 to 5 minutes, the test specimen can be removed from the mold heated to 100 ° C. after approx. 1.5 hours. After tempering at 110 ° C for 24 hours, a soft elastomer (Shore A: 40) with an elasticity of approx. 28% is obtained.
- Example 4 (Comparative Example to Use Example 3)
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
Die vorliegende Erfindung betrifft neue, als Homologen- und isomerengemisch vorliegende, Alkylsubstituierte Phenylendiamine, ein Verfahren zu ihrer Herstellung, sowie ihre Verwendung als Kettenverlängerungsmittel bei der Herstellung von Polyurethankunststoffen.The present invention relates to new alkyl-substituted phenylenediamines which are present as a homolog and isomer mixture, a process for their preparation and their use as chain extenders in the production of polyurethane plastics.
Aromatische Diamine stellen eine bekannte Verbindungsklasse dar. Die einfachsten Vertreter dieser Verbindungsklasse, d. h. die isomeren Phenylen- und Toluylendiamine sind jedoch mit dem Nachteil behaftet, daß es sich um bei Raumtemperatur kristalline Substanzen handelt, und die daher als Reaktionspartner für organische Polyisocyanate, beispielsweise als Kettenverlängerungsmittel bei der Herstellung von Polyurethankunststoffen kaum Eingang in die Praxis gefunden haben.Aromatic diamines represent a known class of compounds. The simplest representatives of this class of compounds, i. H. However, the isomeric phenylene and toluenediamines have the disadvantage that they are substances which are crystalline at room temperature, and which have therefore found little use in practice as reactants for organic polyisocyanates, for example as chain extenders in the production of polyurethane plastics.
In der US-PS 2934 571 wird die Herstellung von langkettigen Dinitro-alkyl-benzolen beschrieben, die gemäß US-PS 2 986 576 zu den entsprechenden Diaminen weiterverarbeitet werden können. Bei den gemäß US-PS 2 934 571 als Ausgangsmaterial eingesetzten Alkylbenzolen handelt es sich, wie insbesondere den Ausführungsbeispielen zu entnehmen, um weitgehend definierte Verbindungen, die insbesondere eine verzweigte Oligopropylen-Seitenkette aufweisen. Zur Nitrierung dieser Kohlenwasserstoffe wird in der Vorveröffentlichung ein spezielles Nitrierverfahren vorgeschlagen, da klassiche Nitrierverfahren offensichtlich bei der Nitrierung der gemäß Vorveröffentlichung einzusetzenden Kohlenwasserstoffe zu den entsprechenden Dinitro-alkyl-benzolen versagen. Trotz des aufwendigen Verfahrens unter Mitverwendung von Schwefeltrioxidhaltiger Schwefelsäure entstehen beim Verfahren der US-PS 2 934 571 störende Restanteile an Mononitroverbindungen, wie eigene Untersuchungen zur Dinitrierung eines gemäß Beispiel V der Vorveröffentlichung hergestellten Dodecylbenzols belegen. Die Weiterverarbeitung dieser Zwischenstufe zu Diaminen führt zwangsläufig zu Diaminen mit einem unerwünschten Gehalt an Monoaminen, so daß die Diamine als Kettenverlängerer bei der Herstellung von Polyurethankunststoffen' weitgehend unbrauchbar sind. Hierdurch wird auch verständlich, daß die Verfahrensprodukte der genannten Vorveröffentlichungen bislang keinen Eingang in die technische Polyurethanchemie finden konnten.US Pat. No. 2,934,571 describes the production of long-chain dinitro-alkyl-benzenes which can be processed further to give the corresponding diamines in accordance with US Pat. No. 2,986,576. The alkylbenzenes used as starting material according to US Pat. No. 2,934,571, as can be seen in particular from the exemplary embodiments, are largely defined compounds which in particular have a branched oligopropylene side chain. For the nitration of these hydrocarbons, a special nitration process is proposed in the prior publication, since conventional nitration processes obviously fail when nitrating the hydrocarbons to be used according to the prior publication to the corresponding dinitro-alkyl-benzenes. In spite of the complex process involving the use of sulfuric acid containing sulfur trioxide, the process of US Pat. No. 2,934,571 gives rise to disruptive residual fractions of mononitro compounds, as shown by our own investigations into the dinitration of a dodecylbenzene prepared according to Example V of the prior publication. The further processing of this intermediate to diamines inevitably leads to diamines with an undesirable content of monoamines, so that the diamines are largely unusable as chain extenders in the production of polyurethane plastics. This also makes it understandable that the process products of the aforementioned prior publications have so far not been able to find their way into technical polyurethane chemistry.
Es war die Aufgabe der vorliegenden Erfindung, einfache aromatische Diamine, d. h. solche, die nur einen aromatischen Kern und zwei aromatisch gebundene primäre Aminogruppen aufweisen, zur Verfügung zu stellen, welche nach einem einfachen Verfahren zugänglich und bei Raumtemperatur flüssig sind, die bei Raumtemperatur keine Kristallisationstendenz aufweisen, die ohne störende Anteile an Monoaminen sind, und die daher problemlos als Reaktionspartner für organische Polyiosocyanate bei der Herstellung von Polyisocyanat-Additionsprodukten einsetzbar sind. Diese Aufgabe konnte durch die Bereitstellung der nachstehend näher beschriebenen erfindungsgemäßen Verbindungen gelöst werden.It was the object of the present invention to provide simple aromatic diamines, i.e. H. to provide those which have only one aromatic nucleus and two aromatically bound primary amino groups, which are accessible by a simple process and are liquid at room temperature, which have no tendency to crystallize at room temperature, which have no disruptive amounts of monoamines, and therefore can easily be used as reactants for organic polyiosocyanates in the production of polyisocyanate addition products. This object could be achieved by providing the compounds according to the invention described in more detail below.
Gegenstand der Erfindung sind, als Homologen- und Isomerengemisch vorliegende Diamine der Formel
R für einen gesättigten, geradkettigen, aliphatischen Kohlenwasserstoffrest mit 8-15 Kohlenstoffatomen steht,
und welche durch Dinitrierung und anschließende Hydrierung der Nitrogruppen von, als Homologen- und Isomerengemisch vorliegenden Kohlenwasserstoffen der Formel
and which by dinitration and subsequent hydrogenation of the nitro groups of hydrocarbons of the formula present as a mixture of homologs and isomers
Gegenstand der Erfindung ist auch ein verfahren zur Herstellung dieser neuen Diamine, welches dadurch gekennzeichnet ist, daß man als Homologen- und Isomerengemisch vorliegende Kohlenwasserstoffe der zuletzt genannten Art in an sich bekannter Weise durch Nitrierung in Dinitroverbindungen der Formel
Gegenstand der vorliegenden Erfindung ist auch die Verwendung der neuen Diamine als Kettenverlängerungsmittel bei der Herstellung von Polyurethankunststoffen nach dem Isocyanat-Polyadditionsverfahren.The present invention also relates to the use of the new diamines as chain extenders in the production of polyurethane plastics by the isocyanate polyaddition process.
Ausgangsmaterialien für das erfindungsgemäße Verfahren sind als Homologen- und Isomerengemisch vorliegende Alkylbenzolgemische der Formel
- R für gesättigte, geradkettige aliphatische Kohlenwasserstoffreste mit 8-15, vorzugsweise 10-13 Kohlenstoffatomen steht.
- R represents saturated, straight-chain aliphatic hydrocarbon radicals having 8-15, preferably 10-13 carbon atoms.
Die Herstellung derartiger Alkylbenzol-Gemische erfolgt in an sich bekannter Weise durch Alkylierung von Benzol mit den entsprechenden technischen, linearen Olefingemischen, wie beispielsweise den entsprechenden technischen Oligoethylengemischen oder anderen linearen Oligoolefinen oder mit den entsprechenden technischen linearen Alkylchloridgemischen, wie beispielsweise in Kirk-Othmer, Encyclopedia of Chemical Technology, third edition, Vol. 2, (1978) auf Seiten 50 bis 61 beschrieben.Such alkylbenzene mixtures are prepared in a manner known per se by alkylating benzene with the corresponding technical, linear olefin mixtures, such as, for example, the corresponding technical oligoethylene mixtures or other linear oligo-olefins, or with the corresponding technical linear alkyl chloride mixtures, as for example in Kirk-Othmer, Encyclopedia of Chemical Technology, third edition, Vol. 2, (1978) on pages 50 to 61.
Bei der Durchführung des erfindungsgemäßen. Verfahrens erfolgt die Überführung der Alkylbenzole in die entsprechenden Dinitroverbindungen durch eine an sich bekannte Nitrierungsreaktion beispielsweise im Temperaturbereich von 10 bis 30 °C unter Verwendung von beispielsweise 2-3 Mol konzentrierter Salpetersäure pro Mol Alkylbenzol, wobei die Salpetersäure in Form eines Gemischs mit konzentrierter Schwefelsäure (Nitriersäure) zur Anwendung gelangt. Bei den hierbei anfallenden Alkylsubstituierten Dinitrobenzolen sind gemäß Kernresonanzmessungen über 95% aller Nitrogruppen in meta-Stellung zueinander angeordnet. Außerdem kann davon ausgegangen werden, daß ca. 10-30 Gew.-% der dinitrierten Alkylbenzole 1-Alkyl-2,6-dinitrobenzole und ca. 70-90 Gew.-% 1-Alkyl-2,4-dinitrobenzole darstellen. Diese Isomerenverteilung ist jedoch keineswegs erfindungswesentlich. So wäre es auch beispielsweise möglich, für die nächste Stufe des erfindungsgemäßen Verfahren dinitrierte Alkylbenzole einzusetzen, in denen andere Mengenverhältnisse der genannten Isomeren vorliegen. So könnte : beispielsweise für die nächste Stufe des erfindungsgemäßen Verfahrens auch 1-Alkyl-2,4-dinitrobenzol in 2,6-freier Form eingesetzt werden, wie es beispielsweise durch zweistufige Nitrierung von Alkylbenzol über die Zwischenstufe des zunächst isolierten 1-Alkyl-4-nitrobenzols erhältlich ist.When performing the invention. In the process, the alkylbenzenes are converted into the corresponding dinitro compounds by a nitration reaction known per se, for example in the temperature range from 10 to 30 ° C. using, for example, 2-3 moles of concentrated nitric acid per mole of alkylbenzene, the nitric acid in the form of a mixture with concentrated sulfuric acid ( Nitrating acid) is used. In the case of the alkyl-substituted dinitrobenzenes obtained in this way, according to nuclear magnetic resonance measurements, over 95% of all nitro groups are arranged in a meta position to one another. In addition, it can be assumed that about 10-30% by weight of the dinitrated alkylbenzenes are 1-alkyl-2,6-dinitrobenzenes and about 70-90% by weight of 1-alkyl-2,4-dinitrobenzenes. However, this isomer distribution is by no means essential to the invention. It would also be possible, for example, to use dinitrated alkylbenzenes for the next stage of the process according to the invention, in which other proportions of the isomers mentioned are present. For example, 1-alkyl-2,4-dinitrobenzene in 2,6-free form could also be used for the next stage of the process according to the invention, as is the case, for example, by two-stage nitration of alkylbenzene via the intermediate stage of the initially isolated 1-alkyl-4 -nitrobenzene is available.
Durch die Verwendung der erfindungswesentlichen Alkylbenzolgemische als Ausgangsmaterial werden die Dinitroalkylbenzolgemische ohne störende Mononitroanteile erhalten, wie der jeweils ermittelte Gehalt an Nitrogruppen, sowie dünnschichtchromatographische Untersuchungen der Nitrierungsprodukte belegen. Die so erhaltenen Dintroalkylbenzolgemische sind daher ausgezeichnet für eine direkte Weiterverarbeitung zu den erfindungsgemäßen Diaminen geeignet, ohne daß aufwendige Renigungsoperationen erforderlich werden, die insbesondere im Fall einer Entfernung der Mononitroverbindungen durch Destillation unter technischen Bedingungen unkalkulierbare Gefahren wegen der leichten Zersetzlichkeit von aromatischen Nitroverbindungen unter thermischer Belastung mit sich bringen würden.By using the alkylbenzene mixtures essential to the invention as the starting material, the dinitroalkylbenzene mixtures are obtained without disruptive mononitro fractions, as evidenced by the content of nitro groups determined in each case, and by thin-layer chromatographic studies of the nitration products. The dintroalkylbenzene mixtures thus obtained are therefore excellently suitable for direct further processing to give the diamines according to the invention, without the need for complex purification operations which, in particular in the case of removal of the mononitro compounds by distillation under technical conditions, involve incalculable dangers because of the easy decomposability of aromatic nitro compounds under thermal stress would bring themselves.
Die nächste Stufe des erfindungsgemäßen Verfahrens besteht in der an sich bekanten Hydrierung der Nitrogruppen zu den entsprechenden primären Aminogruppen beispielsweise unter Verwendung von Raney-Nickel als Hydrierungskatalysator bei beispielsweise 20-60 °C und einem Wasserstoffdruck von beispielsweise 20 bis 40 bar.The next stage of the process according to the invention consists in the known hydrogenation of the nitro groups to the corresponding primary amino groups, for example using Raney nickel as a hydrogenation catalyst at, for example, 20-60 ° C. and a hydrogen pressure of, for example, 20 to 40 bar.
Die bei dieser Hydrierung anfallenden erfindungsgemäßen Diamine der obengenannten Formel entsprechen selbstverständlich bezüglich der Stellung der Aminogruppen den bezüglich der Stellung der Nitrogruppen gemachten Ausführungen und bezüglich der Natur des Restes R den bei der Beschreibung der zu ihrer Herstellung einzusetzenden Atkytbe.nzoten gemachten Ausführungen.The diamines of the above formula according to the invention obtained in this hydrogenation naturally correspond with regard to the position of the amino groups to the statements made with regard to the position of the nitro groups and with regard to the nature of the radical R to the descriptions in the description of the Atkytbe to be used for their preparation . nzoten made statements.
Die erfindungsgemäßen Diamine stellen bei Raumtemperatur flüssige Substanzen dar, die keinerlei Kristallisationsneigung erkennen lassen, und die keinerlei störende Anteile an monofunktionellen Aminen enthalten. Es handelt sich bei den erfindungsgemäßen Verbindungen aus diesem Grund um wertvolle Kettenverlängerungsmittel bei der Herstellung von Polyurethankunststoffen nach dem Isocyanat-Polyadditionsverfahren.The diamines according to the invention are substances which are liquid at room temperature and which show no tendency to crystallize and which contain no disruptive proportions of monofunctional amines. For this reason, the compounds according to the invention are valuable chain extenders in the production of polyurethane plastics by the isocyanate polyaddition process.
Bei der erfindungsgemäßen Verwendung der neuen Diamine werden diese im allgemeinen mit NCO-Präpolymeren unter Einhaltung eines NCO/NH2-Äquivalentferhältnisses von 0,7 : bis 1,3 : 1, vorzugsweise 0,9 1 bis 1,1 : 1, in an sich bekannter Weise zur Reaktion gebracht. Bei den hierbei einzusetzenden NCO-Präpolymeren handelt es sich um an sich bekannte Umsetzungsprodukte der in der Polyurethanchemie an sich bekannten Diisocyanate mit unterschüssigen Mengen an Polyhydroxylverbindungen, insbesondere Polyhydroxypolyestern oder Polyhydroxypolyethern eines zwischen 300 und 10000, vorzugsweise 1 000 und 4000 liegenden Molekulargewichts und einer (im Falle der Verwendung von Gemischen von Polyhydroxylverbindungen mittleren) Hydroxylfunktionalität von 2 bis 8, vorzugsweise 2 bis 3. Die neuen erfindungsgemäßen Diamine können jedoch auch vorteilhaft nach einem Einstufen-Verfahren bei der Herstellung von Polyurethanen verwendet werden, indem sie einer Polyhydroxylverbindung oder einem Gemisch von Polyhydroxylverbindungen der beispielhaft genannten Art zugemischt werden, worauf dieses Gemisch mit den bekannten Polyisocyanaten der Polyurethanchemie unter Einhaltung eines Äquivalentverhältnisses zwischen Isocyanatgruppen und gegenüber Isocyanatgruppen reaktionsfähigen Gruppen von ca. 0,8 : 1 bis 1,2 : 1, insbesondere 1 : 1 zum hochmolekularen Polyurethan umgesetzt wird. Dies ist im Falle der neuen erfindungsgemäßen Diamine insbesondere deswegen möglich, weil die ihnen fehlende Kristallisationstendenz auch auf die hierbei gebildeten Polyharnstoffe übertragen wird, so daß bei einem solchen Eintopf-Verfahren nicht mit unerwünschten Ausscheidungen von Polyharnstoffen gerechnet werden muß. Selbstverständlich kann dieses Verfahren beispielsweise unter Mitverwendung der in der Polyurethanchemie an sich bekannten Hilfs- und Zusatzmittel variiert werden, so daß beispielsweise bei Verwendung der an sich bekannten Treibmittel auch geschäumte Polyurethan-Polyharnstoffe zugänglich sind.When the new diamines are used according to the invention, they are generally mixed with NCO prepolymers while maintaining an NCO / NH 2 equivalent ratio of 0.7: to 1.3: 1, preferably 0.9 1 to 1.1: 1 reacted in a known manner. The NCO prepolymers to be used here are reaction products known per se of the diisocyanates known per se in polyurethane chemistry with deficient amounts of polyhydroxyl compounds, in particular polyhydroxy polyesters or polyhydroxy polyethers having a molecular weight between 300 and 10,000, preferably 1,000 and 4,000 and a (in the case of using mixtures of polyhydroxyl compounds medium) hydroxyl functionality of 2 to 8, preferably 2 to 3. However, the new diamines according to the invention can also advantageously be used a one-step process in the production of polyurethanes can be used by admixing them with a polyhydroxyl compound or a mixture of polyhydroxyl compounds of the type mentioned by way of example, whereupon this mixture with the known polyisocyanates of polyurethane chemistry while maintaining an equivalent ratio between isocyanate groups and groups reactive to isocyanate groups of approx 0.8: 1 to 1.2: 1, in particular 1: 1, is converted to the high molecular weight polyurethane. This is possible in the case of the new diamines according to the invention in particular because the lack of tendency towards crystallization is also transferred to the polyureas formed in this way, so that undesirable excretions of polyureas must not be expected in such a one-pot process. Of course, this process can be varied using, for example, the auxiliaries and additives known per se in polyurethane chemistry, so that foamed polyurethane polyureas are also accessible, for example, when using the known blowing agents.
Die nachfolgenden Beispiele dienen der näheren Erläuterung der Erfindung. Alle Prozentangaben beziehen sich, falls nicht anderslautend erwähnt, auf Gewichtsprozente. Für die dünnschichtchromatograpischen Untersuchungen wurden DC-Fertigplatten, Kieselgel 60F-254, der Firma Merck AG verwendet.The following examples serve to explain the invention in more detail. Unless stated otherwise, all percentages relate to percentages by weight. Ready-to-use plates, silica gel 60F-254, from Merck AG, were used for the thin-layer chromatography investigations.
In diesem Beispiel wird ein Homologengemisch linearer Alkylbenzole eingesetzt, deren Alkylketten eine Länge von 10 bis 13C-Atomen bei einer mittleren Kettenlänge von etwa 12 C-Atomen aufweisen. Das Homologengemisch siedet gemäß ASTM D 86 bei 1 013 mbar zwischen ca. 283 und 313 °C, wobei ca. 50 volumenprozent bis 296 °C übergehen. Es handelt sich um ein Umsetzungsprodukt von Benzol mit einem Gemisch aus linearen C10-C13-Olefinen.In this example, a homologue mixture of linear alkyl benzenes is used, the alkyl chains of which have a length of 10 to 13 C atoms and an average chain length of about 12 C atoms. The homolog mixture boils according to ASTM D 86 at 1,013 mbar between approx. 283 and 313 ° C, with approx. 50 volume percent passing to 296 ° C. It is a reaction product of benzene with a mixture of linear C 10 -C 13 olefins.
In 1,97 kg Alkylbenzolgemisch wird eine Mischung von 1 136 ml 98 %iger Salpetersäure und 1 584 ml 96 %iger Schwefelsäure unter Kühlen so eingetropft, daß die Innentemperatur bei 10 bis 15 °C liegt. Nach Beendigung des Zutropfens wird 3 Stunden bei 25 bis 30 °C nachgerührt. Die organische Phase wird nachfolgend auf 10 kg Eis geschüttet, mit Natriumbicarbonatlösung neutral gewaschen und nochmals mit Wasser nachgewaschen. Die organische Phase wird abgetrennt und von verbleibenden Wasseranteilen durch Zentrifugieren weitgehend befreit. Das so erhaltene, flüssige Dinitroalkylbenzolgemisch wurde ohne weitere Reinigung der nächsten Reaktionsstufe zugeführt.A mixture of 1,136 ml of 98% nitric acid and 1,584 ml of 96% sulfuric acid is added dropwise to 1.97 kg of alkylbenzene mixture with cooling so that the internal temperature is 10 to 15 ° C. After the dropping has ended, the mixture is stirred at 25 to 30 ° C. for 3 hours. The organic phase is subsequently poured onto 10 kg of ice, washed neutral with sodium bicarbonate solution and washed again with water. The organic phase is separated off and any remaining water is largely removed by centrifugation. The liquid dinitroalkylbenzene mixture thus obtained was fed to the next reaction stage without further purification.
Ausbeute : 2,7 kg ; NO2-Gehalt: 27,5 % (Theorie: 27,4 %). Nach dünnschichtchromatograpischen Untersuchungen waren keine Restanteile an Mononitroverbindungen nachzuweisen (Laufmittel 90 Gew.-Tie. Petrolether/10 Gew.-Tle. Ether).Yield: 2.7 kg; NO 2 content: 27.5% (theory: 27.4%). According to thin-layer chromatographic studies, no residual proportions of mononitro compounds were found (eluent 90 parts by weight, petroleum ether / 10 parts by weight ether).
In einem Rührautoklaven werden 672 g der Dinitroverbindung gemäß a) in 1 700 ml Ethanol gelöst und mit 70 g Raney-Nickel versetzt. Bei 40 °C und 20 bis 40 bar Wasserstoffdruck wird bis zum Ende der Wasserstoffaufnahme gerührt. Anschließend wird entspannt, vom Katalysator abfiltriert und das Ethanol abdestilliert. Man erhält 550 g Rohamingemisch, welches als solches oder auch nach destillativer Reinigung für die erfindungsgemäße Verwendung geeignet ist. Das Rohamingemisch weist einen Stickstoffgehalt von 10,06 % (Theorie : 10,1 %) auf.672 g of the dinitro compound according to a) are dissolved in 1,700 ml of ethanol in a stirred autoclave, and 70 g of Raney nickel are added. At 40 ° C and 20 to 40 bar hydrogen pressure, the mixture is stirred until the hydrogen uptake has ended. The pressure is then released, the catalyst is filtered off and the ethanol is distilled off. 550 g of crude amine mixture are obtained, which, as such or after purification by distillation, is suitable for the use according to the invention. The raw amine mixture has a nitrogen content of 10.06% (theory: 10.1%).
200 g Rohamingemisch werden unter vermindertem Druck destilliert. Auf diese Weise können 167 g Diamingemisch als bei 185 bis 204 °C/2,1 mbar siedende Fraktion erhalten werden (Ausbeute : 83,5 %).
Gemäß Beispiel V der US-PS 2 934 571 wurde Dinitrododecylbenzol hergestellt. Das Rohprodukt wies einen N02-Gehalt von nur 18,6 Gewichtsprozent auf. Nach Destillation gemäß Beispiel V der Vorveröffentlichung lag ein Produkt mit einem NO2-Gehalt von 20,0 Gewichtprozent vor. Dünnschichtchromatographische Untersuchungen zeigen erhebliche Anteile an Mononitroverbindungen an, deren Vorliegen aus dem genannten niedrigen NO2-Gehalt hergeleitet werden kann.Dinitrododecylbenzene was prepared in accordance with Example V of US Pat. No. 2,934,571. The crude product had an N0 2 content of only 18.6 percent by weight. After distillation according to Example V, the preliminary ver A product with an NO 2 content of 20.0 percent by weight was available to the public. Thin-layer chromatographic studies show significant proportions of mononitro compounds, the presence of which can be derived from the low NO 2 content mentioned.
Gemäß US-PS 2 986 576, Beispiel V wurde die Nitroverbindung gemäß a) durch Hydrierung in die entsprechende Aminoverbindung überführt.
2000 g eines linearen Polypropylenglykolethers (MG : 2 000, OH-Zahl : 56) werden mit 336 g 1,6-Diisocyanatohexan auf ca. 90 °C erwärmt und bis zu einem NCO-Gehalt von ca. 3,35% bei dieser Temperatur gehalten.2000 g of a linear polypropylene glycol ether (MW: 2,000, OH number: 56) are heated with 336 g of 1,6-diisocyanatohexane to approx. 90 ° C. and up to an NCO content of approx. 3.35% at this temperature held.
500 g dieses NCO-Präpolymeren werden bei ca. 55 °C kurz entgast und innerhalb von 30 Sekunden mit 53 g des erfindungsgemäßen Diamingemisches aus Beispiel 1 vermischt. Nach eine Gießzeit von 4 bis 5 Minuten kann der Probekörper nach ca. 1,5 Stunden aus der auf 100°C erwärmten Form entfernt werden. Nach 24-Stündigem Tempern bei 110 °C erhält man ein weiches Elastomeres (Shore A : 40) mit einer Elastizität von ca. 28 %.500 g of this NCO prepolymer are briefly degassed at about 55 ° C. and mixed with 53 g of the diamine mixture according to the invention from Example 1 within 30 seconds. After a casting time of 4 to 5 minutes, the test specimen can be removed from the mold heated to 100 ° C. after approx. 1.5 hours. After tempering at 110 ° C for 24 hours, a soft elastomer (Shore A: 40) with an elasticity of approx. 28% is obtained.
Entsprechend Beispiel 3 werden 500 g des dortgenannten NCO-Prepolymeren und 53 g des Amingemisches gemäß Beispiel 2 verarbeitet. Es entsteht lediglich eine Flüssigkeit der Viskosität 15 000 mPa.s/20 °C500 g of the NCO prepolymer mentioned there and 53 g of the amine mixture according to Example 2 are processed in accordance with Example 3. Only a liquid with a viscosity of 15,000 mPa.s / 20 ° C is produced
Claims (3)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19813105362 DE3105362A1 (en) | 1981-02-13 | 1981-02-13 | NEW DIAMINES, A METHOD FOR THE PRODUCTION THEREOF, AND THEIR USE AS A CHAIN EXTENSION AGENT IN THE PRODUCTION OF POLYURETHANE PLASTICS |
| DE3105362 | 1981-02-13 |
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| Publication Number | Publication Date |
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| EP0058335A2 EP0058335A2 (en) | 1982-08-25 |
| EP0058335A3 EP0058335A3 (en) | 1983-10-26 |
| EP0058335B1 true EP0058335B1 (en) | 1985-06-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP82100699A Expired EP0058335B1 (en) | 1981-02-13 | 1982-02-02 | Diamines, process for their preparation, and their use as chain extenders in the production of polyurethane plastics |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0058335B1 (en) |
| JP (1) | JPS57150644A (en) |
| CA (1) | CA1207340A (en) |
| DE (2) | DE3105362A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE3833440A1 (en) * | 1988-10-01 | 1990-04-05 | Hoechst Ag | POLYHARM AND FILM MADE OF AT LEAST ONE MONOMOLECULAR LAYER OF A POLYHARM |
| CA2020500A1 (en) * | 1989-07-28 | 1991-01-29 | Robson Mafoti | Process for the preparation of polyurea-polyurethane elastomers |
| DE19614270A1 (en) * | 1996-04-11 | 1997-10-16 | Bayer Ag | Homologous and isomeric mixtures of cycloaliphatic diisocyanates and their use as structural components in the production of polyisocyanate addition products |
| DE19627825A1 (en) * | 1996-07-10 | 1998-01-15 | Bayer Ag | Process for the preparation of polyisocyanates containing isocyanurate groups, the compounds obtainable by this process and their use for the preparation of polyisocyanate addition products |
| KR100542131B1 (en) * | 2003-01-29 | 2006-01-11 | 김용배 | Polyimide resin for non-rubbing vertically alignment materials and preparation method thereof |
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| US2934571A (en) * | 1958-02-06 | 1960-04-26 | Atlantic Refining Co | Dinitrated aromatic compounds and method for their production |
| BE575369A (en) * | 1958-02-06 | |||
| US4218543A (en) * | 1976-05-21 | 1980-08-19 | Bayer Aktiengesellschaft | Rim process for the production of elastic moldings |
| JPS5323936A (en) * | 1976-08-12 | 1978-03-06 | Mitsui Toatsu Chem Inc | Preparation of phenylenediamines |
-
1981
- 1981-02-13 DE DE19813105362 patent/DE3105362A1/en not_active Withdrawn
-
1982
- 1982-01-28 CA CA000395138A patent/CA1207340A/en not_active Expired
- 1982-02-02 EP EP82100699A patent/EP0058335B1/en not_active Expired
- 1982-02-02 DE DE8282100699T patent/DE3264352D1/en not_active Expired
- 1982-02-12 JP JP57019864A patent/JPS57150644A/en active Granted
Non-Patent Citations (1)
| Title |
|---|
| Katalysatoren, Tenside und Mineralöladditive von J. Falbe und K. Hasserodt, Georg Thieme Verlag, Stuttgart 1978 * |
Also Published As
| Publication number | Publication date |
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| JPH0216292B2 (en) | 1990-04-16 |
| EP0058335A2 (en) | 1982-08-25 |
| DE3105362A1 (en) | 1982-09-02 |
| CA1207340A (en) | 1986-07-08 |
| DE3264352D1 (en) | 1985-08-01 |
| JPS57150644A (en) | 1982-09-17 |
| EP0058335A3 (en) | 1983-10-26 |
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